Pigments of the perylene tetracarboxylic acid diimide series

ABSTRACT

N,N&#39;&#39;-BIS-(1,2,4-TRIAZOL-5-YL)-PERYLENE-3,4,9,10-TETRACARBOXYLIC ACID DIMIDE OPTIONALLY SUBSTITUTED IN 3-POSITION OF THE TRIAZOLE RINGS ARE DISCLOSED. THE CLAIMED COMPOUNDS ARE HIGHLY VALUABLE PIGMENTS WHICH ARE DISTINGUISHED BY GOOD FASTNESS TO HEAT, LIGHT, MIGRATION, OVERVARNISHING AND SOLVENTS. THEIR USE IN HIGH-MOLECULAR ORGANIC MATERIAL, E.G. LACQUERS, PLASTIC MATERIALS, SPINMASSES FOR SYNTHETIC FIBRES OF PRINTING PASTE, ARE DESCRIDED.

. S t Patent i 647 8. diphgnylene oxide, diphenyl, or mixtures thereof. When ri ine is used, 't d 1 PIGMENTS OFTHE PE RYLENE TETRACAR- 5 b 3 a W pqrfm-m the BOXYLIC ACID DIIMIDE SERIES ensa a 9 t 6 normal bollmg P 1n p su e Georg Anton Klein, Bottmingen, Basel-Land, Switzerland, vessels expedlently at 200 to assignor to Ciba-Geigy AG, Basel, Switzerland 5 The novel compoundsaccordmg to the invention are No Drawing Filed Oct. 24, 1969, No. 369,367 suitable for the coloring of high-molecular organic ma- Claims priority application Switzerland, N0 5, 196g, terials, for example for the pigmenting of lacquers, also 1 4 0 metallic effect lacquers, plastic materials such as hard or Int. Cl. C07d 55/06 plasticizer-containing polyvinyl chloride, polyurethane,

US. Cl. 260-281 9 Claims 10 polycarbonate, polystyrene, polyacrylonitrile; for the spindyeing of synthetic fibers; or as printing paste. The pigment can be used directly or after preparing it in a finely ABSTRACT OF THEDISC O divided form. The compound can also be used as vat N,N-bis-(1,2,4-triazol-5-yl)-perylene 3,4,9,l0 tetradye.

carboxylic acid diimide optionally substituted in 3-position In the follOWlIlg non-llmitaflon examples, the temperaof the triazole rings are disclosed. The claimed compounds res a e given in degrees Centigrade.

are highly valuable pigments which are distinguished by good fastness to heat, light, migration, overvarnishing and EXAMPLE 1 solvents. Their use in high-molecular organic material, (a) To a flask fitted with thermometer, stirrer and dise.g. lacquers, plastic materials, spinmasses for synthetic tillation attachment and containing 150 g. of quinoline, fibres or printing pastes, are described. 10.6 g. of zinc acetonyl acetonate are added with stirring;

the flask is heated to about 237 until pure quinoline distills off and then cooled to 200. Then 8.0 g. of perylene- The invention concerns novel pigments of the perylene 3,4,9,10-tetracarboxylic acid dianhydride is added and tetracarboxylic acid diimide series, a process for the proheated to the boiling point of the quinoline; 8.0 g. of duction thereof, and the use of these pigments for pig- S-amino-S-methyl-triazole-1,2,4 is added to the 200 hot menting high-molecular organic material. suspension and stirred for to minutes between 200 Pigments of the perylene tetracarboxylic acid diimide and 210. The mixture is then cooled to 100, filtered by series are known; few of them, however, are technically suction under a vacuum of 15 mm. Hg, and the red residue useful. Surprisingly, it has now been found that compounds 30 is Washed t 250 of m a ol- After bringi g to th of the formula boil in 100 ml. of o-dichlorobenzene, it is filtered hot with in which R represents hydrogen, an alkyl group having a water-jet vacuum pump, washed with ml. of o-dichlo- 1 to 3 carbon atoms or an optionally substituted phenyl 45 robenzene and 200 ml. of methanol and dried in vacuum group, in particular however the methyl group, are highly at valuable pigments which are distinguished by good fast- The 14.3 g. of N,N-bis-(3-methyl-l,2,4-triazol-5-yl)- mess to heat, light, migration, overvarnishing and solvents. perylene-3,4,9,l0-tetracarboxylic acid diimide thus ob- When the substituent R represents a substituted phenyl tained are ground for two hours in a ball mill (1 liter havgroup, substituents thereof are halogen, preferably chlo- 50 ing 3.6 kg. of steel balls of 1.5 cm. diameter) with g. of rine or bromine, and/or alkyl and/or lower alkoxy groups, calcium chloride and 5.5 g. of special petroleum (BJP. such lower aliphatic groups having from 1 to 4 carbon 165-200). Then the ground material is suspended in atoms. 500 ml. of 1 N hydrochloric acid, stirred for one hour at The compounds are produced according to the invention then filtered with a water-jet vacuum pump, washed by condensation of perylene-3,4,9,10-tetracarboxylic acid 5 with 1 liter of hot water and dried in vacuum at 60. There or a reactive acid derivative thereof, in particular the are thus obtained 11 g. of a bluish red pigment having anhydrides, with a 3-amino-l,2,4-tn'azole which is in its excellent fastness to light, migration, overvarnishing, heat S-position unsubstituted or substitute-d by a lower alkyl and solvents. group or an optionally substituted phenyl group. For this Bluish red pigments of equal quality are obtained when reaction, if necessary, condensation agents are used, such 60 the 8 g. of 3-amino-5-methyl-triazole-1,2,4 are replaced as hydrochloric acid, concentrated acetic acid, anhydrous by an equivalent amount of one of the following zinc chloride, or zinc or cadmium salts of organic carcompounds:

boxylic acids, e.g. zinc formate, zinc acetate, zinc stearate,

cadmium acetate or the zinc salts of benzoic acid, phthalic (b) acid, phenyl acetic acid and nicotinic acid. Zinc acetyl 65 (c) t acetonate is particullary suitable for this purpose; when (d) 3'ammo's'propyl'lzi4'tnazole' it is present, the reaction proceeds rapidly and with a good EXAMPLE 2 yield. In general, 0.1 to 1 mol of zinc acetyl acetonate per mol of perylene tetracarboxylic acid is used for the con- (a) In a round-bottomed flask fitted with a distillation densation; more of the condensation agent, however, can 70 attachment, g. of quinoline, 2.3 g. of zinc acetate, be added. Preferably the condensation is performed in 4.0 g. of perylene tetracarboxylic acid-3,4,9,10-dianhyhigh-boiling solvents such as quinoline, trichlorobenzene, dride and 4.0 g- Of 3-a111iI10-5-P11eny1-1,2,44Iial016 heated to 230 and kept for 30 minutes between 210 and 220. Then'the reaction mixture is cooled to 100, filtered through a suction filter at a vacuum of 15 mm. Hg; the residue is Washed out with three portions of methanol of 50 ml. each, then boiled in 100 ml. of glacial acetic acid for minutes,removed by filtration, washed with 200 ml. of hot water and dried for 12 hours at 60 in a vacuum of 15 mm. Hg. 1

After being treated as described in Example 1, para graph 2, 5.6 g. of pigment are obtained which has very 10 good properties.

dilaurate, 0.3 g. of a phosphate stabilizer, and 0.7 g. of the pigment obtained according to Examplel by condensing perylene tetracarboxylic acid-3,4,9,IO-dianhydride and 3-amino-5-methyltriazole-1,2,4 are mixed and worked up for 15 minutes on a set of mixing rollers having a temperature of 160. Then a sheeting 0.4 mm. thick is formed on a sheeting calender. The bluish red coloring is heat stable and fast to migration and light.

I claim:

1. A pigment of the formula Beautiful bluish red pigments of similar quality and in good yield are also obtained when in the above-described procedure, the 3-amino-5-phenyl-1,2,4-triazole is replaced by an equivalent amount of EXAMPLE 3 4 g. of N,N'-bis-(3-phenyl-l,2,4-triazolyl-5)-perylene tetracarboxylic acid-3,4,9,10-diimide, 36 g. of aluminum hydroxide, g. of linseed oil varnish of medium viscosity and 0.2 g. of cobalt linoleate are mixed and ground on a three-roller mill. A printing ink is obtained which produces bluish red prints on paper having good light fastness.

EXAMPLE 4 To g. of a stoving lacquer consisting of 58.5 g. of a 6% solution of a coconut fatty acid alkyd resin in xylene, 23 g. of a 65% solution of a melamin resin in butanol, 17 4 g. of xylene and 1.5 g. of butanol, there are added 1 g. of the pigment produced according to Example 1 and 5 g. of titanium dioxide. After grinding the mixture for 48 hours in a ball mill, the lacquer thus pigmented is sprayed onto a cleaned metal surface. The bluish red coating, after 50 stoving at has very good fastn'ess to light, overlacquering and Weathering.

EXAMPLE 5 in which R represents hydrogen, of from 1 to 4 carbon atoms, or a phenyl radical any substituent of which is selected from lower alkyl, lower alkoxy and halogen.

2. A compound as defined in claim 1, wherein R represents methyl.

3. A compound as defined in claim 1, wherein -R repre-. sents hydrogen.

4. A compound as defined in claim 1, wherein R represents ethyl.

5. A compound as defined in claim 1, whereinR represents phenyl.

6. A compound as defined in claim 1, wherein R represents p-chloro-phenyl. v

7. A compound as defined in claim 1, wherein R repre sents p-methyl-phenyl.

8. A compound as defined in claim 1, wherein R represents p-methoxy-phenyl.

9. A compound as defined in claim 1, wherein R represents p-bromo-phenyl.

References Cited UNITED STATES PATENTS 3,357,983 12/1967 Weener et a1 26028l 3,332,931 7/1967 Braun 260-281 X 3,546,222 12/1970 Irving etal 260--249.6

FOREIGN PATENTS 894,859 4/1962 Great Britain 260-281 DONALD G. DAUS, Primary Examiner US. 01. X.R.

834; 106288 0; 260 37 NP, 37 N, 308 R 

